Novel oximecarbamates

ABSTRACT

NEW COMPOUNDS OF THE FORMULA:   R1-C(-R2)=N-OOC-NH-R3   WHEREIN R1 IS EITHER LOWER-ALKYLTHIO, AR(LOWER-ALKYL)THIO, ARYLTHIO OR LOWER-ALKENYLTHIO; R2 IS R1 OR CHLORO; AND R3 IS LOWER-ALKYL. THE COMPOUNDS ARE USEFUL AS NEMATOCIDES, INSECTICIDES AND ACARICIDES.

United States Patent 3,632,621 NOVEL OXIMECARBAMATES Roger WilliamsAddor, Pennington, and Frank Albert Wagner, Jr., Hopewell, N.J.,assignors to American Cyanamid Company, Stamford, Conn. No Drawing.Filed Jan. 30, 1968, Ser. No. 701,572 Int. Cl. C07'c 131/00 US. Cl.260-453 R 7 Claims ABSTRACT OF THE DISCLOSURE New compounds of theformula:

C=NO( iNHR wherein R is either lower-alkylthio, ar(lower-alkyl)thio,arylthio or lower-alkenylthio; R is R or chloro; and R is lower-alkyl.The compounds are useful as nematocides, insecticides and acaricides.

This invention relates to and has for its object the provision of newoxime carbamates. It relates further to the provision of pesticidalcompositions containing said new ozime carbamates and, still further, tothe use of these compositions as insecticides, acaricides andnematocides.

The compounds according to this invention are represented by thefollowing Formula I:

wherein R is either lower-alkylthio, ar(lower-alkyl)thio, arylthio orlower-alkenylthio; R is R or chloro; and R is lower-alkyl.

The term lower-alkyl includes straight, branched and cyclic saturatedhydrocarbon radicals having up to seven carbons, as exemplified bymethyl, ethyl, n-propyl, nbutyl, sec.-butyl, amyl, sec-amyl, n-hexyl,cyclohexyl and n-heptyl.

The term ar(lower-alkyl) includes monocyclic and bicyclic radicalshaving from one to six carbon atoms in the alkyl radical. The arylradicals may 'be phenyl or naphthyl or lower-alkyl substituted analoguesthereof. Preferred ar(lower-alkyl) are benzyl and phenethyl radicals.

The term ary includes such aryl moieties as were described in thepreceding paragraph.

The term lower-alkenyl includes alkenyl radicals of one to seven carbonatoms as for example allyl and methallyl as well as alkenyl radicalshaving an aryl substituent, e.g. styryl or cinnamyl.

Among the compounds which are included in the scope of Formula I are:

O-(methylcarbamoyl) methylthiochloroformaldehyde oximeO-(propylcarbamoyl) butylthiochloroformaldehyde oxime O-(ethylcarbamoyl)butylthiochloroformaldehyde oxime O-(propylcarbamoyl)benzylthiochloroformaldehyde oxime 3,632,621 Patented Jan. 4, 1972 Thecompounds of this invention are prepared by reacting at least one moleof a carbamate of dichloroformaldehyde oxime represented by the FormulaII:

with one mole of a mercaptan of the Formula III:

R SH III wherein R and R are as defined above. When the oxime is reactedwith only one mole of mercaptan, the product which is obtained is thatof Formula I wherein R is chloro. When two moles of mercaptan arereacted, the

compounds of Formula I wherein R is not chloro, are' obtained. When theoxime is reacted with two moles of mercaptan, it is possible to employone mole each of different mercaptans. In this case, the mercaptans canbe reacted either concurrently or sequentially.

Preferably, the reaction is carried out in the presence of a 'base at atemperature ranging from minus 50 to plus 30 C. It is desirable toemploy an inert reaction medium such as a lower alkanol, an alkyl ether(e.g., ethyl ether), a cyclic ether (e.g., tetrahydrofuran), ahalogenated aliphatic hydrocarbon (e.g., chloroform), a lower alkenone(e.g., acetone), or an aromatic solvent such as benzene.

A basic material is necessary to effect the addition of the mercaptansto the carbamate of dichloroformaldehyde oxime. Among the suitable basicmaterials are sodium hydroxide, potassium hydroxide, triethylamine,tributylamine, dimethylaniline, diethylene diamine and potassiumt-butoxide.

The carbamate of dichloroformaldehyde oxime used as a starting materialfor the preparation of the compounds of Formula I of this invention aredisclosed and claimed 'in copending application Ser. No. 640,330, filedMay 22, 1967 (Case No. 21,892). These compounds are convenientlyprepared by reacting one mole of phosgene oxime with a mole of alower-alkyl isocyanate. The reaction is conducted in the presence of asolvent such as benzene and from 1 to 10% by weight of a basic catalystsuch as triethylamine.

The compounds of Formula I have pesticidal activity and can be used asinsecticides and soil nematocides in the protection of decorativefoliage and agronomic crops from infestations of insects and ascaridssuch as the Southern Ar myworm, Nasturtium Aphids, Two-Spotted SpiderMite, Confused Flour Beetle, Large Milkweed Bug, German Cockr'oach, andthe Southern Corn rootworm. For use as an insecticide, nematocide oracaricide the compounds of Formula I are incorporated in an effectiveamount (generally btween about 0.1 and 95.0% by weight of thecomposition) into an active formulation containing a conventionallyuseful diluent. The diluent maybe chosen so as to give a solid or liquidformulation, Solid diluents such as talc, kaolin, attapulgite anddiatomateous earth are preferably in the form of wettable powders whichmay in themselves exert insecticidal activity or be 'biologicallyinactive. Likewise, liquid formulations such as water emulsions orsolutions or suspensions in liquid hydrocarbons (e.g. xylene ordeodorized kerosene) may be based upon insecticidally inert liquiddiluents or be a combination of such diluents with insecticidally activeliquid material. The particular formulation which is chosen depends uponfactors and conditions which are normally relied upon to determine thetype of formulation and the concentration of active components.

The following examples are presented to further illustrate the presentinvention.

EXAMPLE A Preparation of O-methylcarba'moyl dichloroformaldehyde oximeTo a stirred mixture of 48.5 parts of distilled phosgene oxime and 28.4parts (by volume) of methyl isocyanate in 150 parts (by volume) ofbenzene is slowly added ca. 5 parts (by volume) of triethylamine untilfurther addition produces no noticeable exotherm. After two hours, anadditional parts (by volume) of methyl isocyanate is added and themixture is allowed to stand overnight.

The resultant mixture is concentrated in vacuo and partitioned between200 parts .(by volume) of ether and parts of water. The ether layer iswashed with dilute hydrochloric acid, saturated sodium chloride, driedover magnesium sulfate, treated with activated charcoal, andconcentrated in vacuo to yield 55.1 grams (76% based on phosgene oxime)of orange oil which crystallizes on seeding and cooling; melting pointca. 25 C. This material, combined with another 19.7 grams of crudeproduct of similar quality in 200 milliliters of ether, is Washed with20 parts (by volume) of 5% potassium hydroxide solution (dark wash) andwashing is completed as before. The dry ether solution is brought to thecloud point with 150 milliliters of petroleum ether, cooled to 0 C. andseeded. Further slow cooling to -55 C. yields light yellow crystalswhich are collected and washed with gigt rjolelm ether; 55.1 grams,melting point 31.5 C.-

Purification of O-methylcarbomyl dichloroformaldehyde oxime is alsoachieved by passing crude product through a film molecular still at4070/ .005 mm. Hg. Under these conditions, phosgene oxime carbamatecollects as a colorless solid on the condenser and is removed bysubsequent replacement of cold with hot water. Unreacted phosgene oximecollects in the Dry Ice traps. A sample of this material crystallizesfrom 1:1 ether petroleum ether as fine White crystals, melting point32.8 C.-33.6 C. i

.4 EXAMPLE B Preparation of O ethylcarbamoyl dichlorofarmaldehyde oximeEmploying the procedure of Example A, a mixture of equimolar amounts ofdistilled phos-gene oxime and ethyl isocyanate in benzene is treatedwith triethylamine until no further exotherm is observed with theaddition of small amounts of the triethylamine. After standing, excessethyl isocyanate is added to the reaction mixture and the mixture ispermitted to stand at room temperature for several hours. The mixture isthen concentrated under reduced pressure, partitioned between ether andwater, the ether layer is separated from the water and washed withhydrochloric acid followed by saturated sodium chloride, then dried andconcentrated under vacuum. 0- ethylcarbomyl dichloroformaldehyde oximeis recovered in good yield In similar fashion, O-isopropylcarbamoyldichloroformaldehyde oxime is prepared employing the above procedure,but substituting isopropyl isocyanate for methyl isocyanate.

EXAMPLE 1 Preparation of O-(methylcarbamoyl ethylthiochloroformyldehydeoxime c1 0 CgH S( 3:NO-( ,-NHCH A mixture of 1.86 parts of ethanethioland 3.37 parts of potassium t-butoxide in 25 parts of methanol was addedslowly to 5.13 parts of phosgene oxime methylcarbamate in 25 parts ofmethanol maintained at -15 C. by a cooling bath. After addition iscomplete, the mixture was allowed to come to room temperature. Themethanol was removed under vacuum and the residue was partitionedbetween ml. of etherbenzene and water. The organic phase was washedsuccessively with dilute potassium hydroxide and saturated saltsolution. After filtering through magnesium sulfate, the mixture wasconcentrated in vacuo to give 4.54 parts of oil which crystallized oncooling. Recrystallization from etherhexane gave 3.15 parts (53%) ofcolorless crystals, M.P. 37.0-38.0 C. A sample recrystallized again fromanalysis melted at 37.5-38.5 C.

EXAMPLE 2 Preparation of O-(methylcarbamoyl)methylthiochloroformaldehyde oxime I ll CH3SC=NO-C-NHCH3 In a taredmixture of 17.5 g. (0.102 mole) of phosgene oxime methylcarbamate in 100ml. of benzene was collected 6.2 g. (0.139 mole) of methyl mercaptan.The mixture was ice-cooled and 10.4 g. (0.102 mole) of triethylamine in25 ml. of benzene was added with good stirring over 20 minutes. Afteranother hour, the mixture was diluted with ether and washed 5 times withwater. Drying and concentrating in vacuo left 15.7 g. (84%) of yellowoil which completely crystallized on seeding; melting point, 58-63 C. Asample was twice recrystallized from ether at about 70 C. and vacuumsublimed at 55-60 C./0.2 mm. to give colorless crystals, melting point63.2-64.8 0.

EXAMPLE 3 Preparation of O-(methylcarbamoyl)benzy-lthiochloroformaldehyde oxime The reaction was carried out in thesame manner as Example 1 replacing ethyl mercaptan with benzylmercaptan. The crude product was recrystallized from toluene ture wasstirred an additional 30 minutes after removing and from atoluene-hexane mixture at l C. to give the cooling bath. The infraredspectrum indicated reaca 61% yield of colorless plates, M.P. 103.0-105.0C. tion was complete. After adding 50 ml. of benzene, the mixture stoodopen overnight. Additional benzene was EXAMPLE 4 5 added and the mixturewas water-washed and dried and Preparation of o-(methylearbamoyl)phenylthi ochloroleft in a beaker. Evaporation of solvent, seeding andformaldehyde oxime further drying of the residue in a vacuum desiccatorgave mostly crystalline solids. Recrystallization from ether gave 8.9 g.(78%) of colorless crystals, M.P. 57.4-58.4 -s o=N-o-c-Nnen. c. and57.0-58.2" 0. as two crops. EXAMPLE 9 The reaction was carried out as inExample 1 replacing ethyl mercaptan with thiophenol. The crude productwas i223:$3 ;fi ;g;?; recrystallized twice from toluene to give a 75%yield of slightly yellow crystals, M.P. 125.0-l27.0 c. 0

EXAMPLE 5 (G2H5S)2C:N-OH-NHOH3 Preparation of O (methylcarbamoyl)allylthiochloroformaldehyde oxime The reaction was carried out in thesame manner as in C1 6 Example 8 replacing methyl mercaptan with ethylmer- H captan. The crude product was recrystallized from ether to givecololrless crystals, M.P. 67.5-67.8 C.

The reaction was carried out in the same manner as EXAMPLE 10 Example 1except that n-propyl mercaptan replaced ethyl Preparation of(omethylcarbamoyloxime) mercaptan and the reaction was run at instead(benzythio) methylthioformaldehyde oxime of -15 C. The crude product wasrecrystallized twlce from ether-hexane at 55 C. to give a 69% yield ofcolorless needles, M.P. 38.5-40.0 c. cm H 30 C:NOCNHCH3 EXAMPLE 6 Q CH2S/ Preparation of O-(methylcarbamoyl) allylthiochloroformaldehyde oxime3r A mixture of 12.4 g. of benzyl mercaptan and 5.4 g. of sodiummethoxide in 100 ml. of methanol was added CH2=CHCHz-SC=N-OC-NHCH3dropwise over a 15 minute period to a stirred mixture of 18.3 g. ofO-(methylcarbamoyl) methylthiochloroformal- The reaction was carried outin the same manner as dehyde oxime as prepared in Example 2 in 50 mL ofExample 1 except that allyl mercaptan replaced ethyl methanol cooled to100 After 30 minutes tha mercaptim and the reaction was run 350 insteadture was allowed to come to room temperature and was of 15 crude Productwas punfiefl by chroma' worked-up as described in Example 1. The productwas P Y slhca gel 115mg methallol m benzene as isolated as a solidshowing strong infrared absorption at the elutlng solvent. Thecrystalline fractions were recrys- 150.0, 1710, and 3400, typical of theoximecarbamate tallized from ether-hexane at -55 C. to give colorlessfunction crystals, M.P. 46.0-48.5 C. EXAMPLE 11 EXAMPLE 7 Insecticidaland acaricidal activity Preparation f 1 b 1) The compounds of thisinvention are tested for activity b t lthi hl f r ald hyd oxime agalnstcommon pests by the followlng procedures.

01 O 1) Southern Armyworm Compounds to be tested are made up as 0.1%solutions The reaction w2 1s carried out in the S.ame manner as asabove. Sieva lima bean leaves are dipped in the test Example 1 replacmgethyl. mercaptan Wlth i solution and set in the hood to dry. When dry,they are Captan and i the P g at placed in four-inch Petri disheswhichhave a moist stead of 15 The.cru o y uct cou no 6 filter paper inthe bottom, and ten third-instar armyworm completely freed of animpurity, but lnfrared and nuclear larvae about long are a d d e d toeach dish. The dishes magnetic resonance spectra attested to thepresence of a are covered and held at R RH After two days largePercentage of the deslred compound 60 mortality counts and estimates ofthe amount of feeding EXAMPLE 8 are made.

(2) Nasturtium Aphids Preparation of O-(methylcarbamoyl)bis-methylthioformaldehyde oxime (Aphis rumicis L.)

The compounds to be tested are made up as 0.1%, (CHBS)ZC:N O (|E NHCH3.01%, and 001% solutions in 65% acetone-35% water. Three inch potscontaining a nasturtium plant two inches About 75 ml. of methylmercaptan was collected in a tall and infested two days before areselected for testing. 3-neck flask containing 10.0 g. (0.059 mole) ofphos- The pots are placed on a turntable (4 r.p.m.) and sprayed geneoxime methylcarbamate. The flask was equipped for two revolutions with a#15 DeVilbiss Atomizer at 20 with a Dry Ice-acetone condenser and cooledwith an p.s.i. air pressure. The spray tip is held about six inchesalcohol bath at -20 C. With the system under nitrogen, from the plantsand the spray is directed so as to give 13.2 g. (0.12 mole) of potassiumt-butoxide was added in complete coverage of the aphids and the plants.The small increments over about 20 minutes. The viscous mixsprayedplants are laid on their side on white enamel trays 7 (9%" X 13%" xwhich have had the edges coated with #50 S.A.E. oil as a barrier.Mortality estimates are made after holding for two days at 70 R, 50%R.H.

(3) Two-spotted Spider Mite (Tetranyclzus telarius I.)

Compounds to be tested are made up as 0.1% solutions in 65% acetone-35%water. Sieva lima bean plants with the first pair of leaves three tofour inches in size are infested about five hours before testing, usingabout 100 to 200 adult mites per leaf. The infested leaves are dipped inthe test solutions (in four-inch crystallizing dishes) for threeseconds, and the plants set in the hood to dry. The treated plants areheld for two days at 80 F., 60% R.H., and the adult mite mortalitycalculated by counting dead and alive adults on one leaf under the lbinocularscope. The other leaf is held an additional five days and thenis examined at 10 power to estimate the kill of eggs and newly-hatchednymphs, giving a measure of ovocidal and residual active, respectively.

(4) Confused Flour Beetle (Tribolium confusum Duv.)

Compounds to be tested are made up as 1.0% dusts by mixing 0.1 gm. ofcompound with 9.9 gm. of Pyrax ABB talc, wetting With 5 ml. of acetoneand grinding in a mortar and pestle until dry. 125 mg. of this 1% dustis then blown into the top of a dust settling tower with a short blastof air at 20 p.s.i. The dust is allowed to settle on 4-inch Petri dishesfor two minutes. The dishes are 8 removed and adult confused flourbeetles are added immediately. The dishes are held for three days at 80F., 60% R.H., following which mortality counts are made.

(5) Large Milkweed Bug (Oncopeltus fasciatus Dall.)

(Blattella germanica L.)

The procedure is the same as for the large Milkweed Bug; however, onlyadult males are used in this test.

(7) Southern corn rootworm Diabrotica undeoimpzmctata h'owardi BarberThe compound is formulated as a dust and incorporated into the soil atthe equivalent of 10 and pounds per 6-inch acre. The soil is sub-sampledinto one-ounce wide mouth bottles, and ten 6- to 8-day 01d rootroomlarvae added to each bottle, which is then capped. Mortality counts aremade after six days at 80 F., R.H.

Test results are summarized in Table I (reported as percent mortality).

TABLE I.PE RCENT MORTALITY Aphids I Rootworm Army- Splder Flour MilkweedGerman worms, mite beetle, bug, cockroach, Lbs. 50 Lbs. 10 Compound 1%1% 01% 001% 01% 1% 1% 1% acres acres CH3 S i) 100 100 100 100 37 100 10090 100 100 G=N- O- C-NH CH CH3S (I? 100 100 100 90 0 100 100 100 50 C=N-O -NHCH CQHsS (III) 100 100 100 0 100 100 100 25 C=N-O-CNHC Ha C 2115 S(H) 0 100 100 50 0 O 45 0 C=N-OCNHCH3 n-C H7S a) 60 100 100 20 81 100100 85 45 C:N O NH C 11 Cl CHz=CH-CHe-S h) 60 100 100 90 0 02 100 10 20C=N- O- -NH C 11;

0 100 100 90 0 0 0 0 0 CH? n C=N O-C-NHC H C1 C=N-O-C-NHCHs t-C HnS O100 100 9 'EXAMPLE 12 Nematocidal activity To demonstrate thenematocidal activity of several representative oxime carbamates againstthe root-knot nematode, test compounds are mixed with a potting soilcontaining root-knot nematodes (Meloidogyne sp.) eggs and larvae. Onequart of soil is placed in a one-gallon stainless steel beaker.Predetermined amounts of the appropriate formulated oxime carbamate ispipetted onto the soil which is then thoroughly mixed on a mechanicalmixer. The treated soil is then distributed between two pint containers.As the containers are being filled, the root-knot nematode inoculum isintroduced into the soil. Qne week What is claimed is: 1. A compound ofthe formula:

wherein R is either lower-alkylthio, loweralkenylthio, benzylthio orphenylthio and R is lower alkyl.

2. A compound of claim 1 wherein R is benzylthio or phenethylthio.

after treatment the soil is planted to a root-knot nematode 3 Th e comound of claim 1 which s O- meth lsusceptible tomato plant. After amonths growlng time carbamoyl) metfiylthi o chloroform a1 dehy dc y thetomato plants are removed from the soil. The roots 4 The com ound ofclaim 1 which is olmeth are washed and examined for nematode injury. Theplants carb'amo Deth fthiochloroformaldeh d y are rated according to thefollowing scale: 5 y y y e OX1 A compound of claim 1,O-(methylcarbamoyl)- 9 p controlallylthiochloroformaldehyde oxime. 1H1ghdegree of control- 6. A compound of claim 1, O-(methylcarbamoyl)- 2-Nocontrolbenzylthiochloroformaldehyde oxime. Rates of application of thetoxicants are at 50, 10 or 5 A ompo nd of claim 1, O-(methylcar-bamoyl)-lbs/acre. The results obtained are reported in Table II.Phenylthiochloroformaldehyde oxime.

TABLE II Root-knot nematode control lbsJa. 101bs.la. 5lbs./a.

CH3S\ O 0 C=N0d-NHOH:

C7H5S (I) 0 o=N0-d-NHOHl C2H6 H 0 C=NOCNHOH;

CZHBS n-CaH1S (I) 0 C=NOd-NHCH:

CH2=CHCHr-S 0 References Cited UNITED STATES PATENTS 3,063,823 11/1962Kiihle et al. 712.6 3,223,733 12/1965 Heiss et al 260--566 FOREIGNPATENTS 5/1966 Belgium 260-566 LEON ZITVER, Primary Examiner G. A.SCHWARTZ, Assistant Examiner US. Cl. XJR.

3,632,621 Dated January 4, 1972 Patent No.

Inventor(s) Roger Williams Addor and Frank Albert Wagner, Jr.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 4, line 19, "ethylcarbomyl" should read ethylc arbamoyl I Signedand sealed this 2nd day of May 1972.

(SEAL) EDWARD ustsrofim, JR. ROBERT GOTTSGHALK Attesting OfficerCommissioner of Patents FORM PC4050 (10-59) USCOMM-DC 60376-P69 [1.5,GOVERNMENT PRINTING OFFICE I969 0-366334

